Highly selective hydroaminomethylation of internal alkenes to give linear amines

Moballigh Ahmed, Raymond P.J. Bronger, Ralf Jackstell, Paul C.J. Kamer, Piet W.N.M. Van Leeuwen, Matthias Beller

Research output: Contribution to journalArticlepeer-review

91 Scopus citations

Abstract

The application of phenoxa-phosphino-modified Xantphos-type ligands (1-9) in the rhodium-catalyzed hydroaminomethylation of internal olefins to give linear amines is reported. Excellent chemo- and regioselectivities have been obtained through the use of 0.1 mol % [Rh(cod)2]BF4/0.4 mol% xantphenoxaphos (1), providing a practical and environmentally attractive synthetic route for the preparation of amines from internal alkenes. For the first time, both functionalized internal olefins and mixtures of internal and terminal olefins have been converted highly selectively into linear amines. Investigations of the effects of the calculated natural bite angles of ligands on hydroaminomethylation shows that the regioselectivity for the linear product follows a similar trend to that seen in the hydroformylation of internal alkenes with the aid of these ligands. Hydroaminomethylation and each of its individual steps were monitored by high-pressure infrared spectroscopy. The results suggest that hydroaminomethylations take place by a sequential isomerization/hydroformylation/amination/hydrogenation pathway.

Original languageEnglish
Pages (from-to)8979-8988
Number of pages10
JournalChemistry - A European Journal
Volume12
Issue number35
DOIs
StatePublished - 4 Dec 2006
Externally publishedYes

Keywords

  • Amines
  • Homogeneous catalysis
  • Hydroaminomethylation
  • Rhodium
  • Xantphos-type ligands

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